Process of separating metals in solution.



UNITED STATES PATENT OFFICE.

HERBERT H. DOW, OF MIDLAND, MICHIGAN, AND WALTER S. GATES, OF WORTHINGTON, ONTARIO, CANADA, ASSIGNORS TO THE ONTARIO NICKEL COMPANY, LIMITED, 0F .WORTHINGTON, CANADA, A CORPORATION.

PROCESS OF SEPADATING DIETALS 1N SOLUTION.

Specification of Letters Patent.

Patented March 2, 1909.

Application filed April 3, 1907. Serial No. 866,159.

"Processes of SeIparating Metals in Solution,

of which the f0 owing is a specification, the principle of the invention being herein explained and the best mode in which we have contemplated apfplying that principle, so as to distinguish it rom other inventions.

Our invention relates to processes of se arating metals and especially to a separatlon of the same, each substantially free of all the others, when contained in a water solution. Said invention consists of steps hereinafter fully described and specifically set forth in the claims.

The improved results obtained by our new process are effected by reason of the fact i which we have discovered that, when a reagent which is capable of precipitating at least one of the metals as an insoluble compound is added to a solution of metalsmore or less of the insoluble com ounds of the other metals are simultaneously precipitated, depending upon the circumstances of. each particular casc if the degrees of insolubility of the insoluble compounds thus precipitated are different and vary among themselves within reasonable limits, and there be present in the original solution enough of the metal, which upon the addition of the rea ent forms the more insoluble compound, to e at least a chemical equivalent of the reagent, then, the more insoluble precipitate is purified of its inclusions of the slightly less insoluble preci itates of the insoluble other metals by subjecting t e original solution and preclpitates to a rolonged agitation by means of which t 1e soluble compound of the metal forming the more insolu- 1e recipitate reacts with the recipitates of t e other metals to form so luble comunds of said other metals and more of the recipitate which is being purified. We fin a particular application for .our improved (process in the seplarating of iron, copper an nickel from eac other, each in the form of a precipitate substantially free of the others, when all are contained in the same original water solution.

We are aware that iron, copper and nickel have been taken from a water solution in the same order and by the same reagents that we use, but we are not aware that products anywhere nearly pure have been obtained in the manner embodying our improved process. However, in fact we do know that large amounts of the valuable metals have been lost in the iron precipitate in other processes.

The fact is well-known that, if two metals are resent in a solution, and one. of the meta forms apreci itateoraninsolublecompound more insolu le than the correspondmg com ound of the second metal, and there is added to the solution the proper amount of a reagent capable of throwing down the first metal as a precipitate, then, said pre cipitate will in many cases carry down with it in insoluble form art of the second metal. This will ha pen, ist, always in case the second meta is also capable of being precipitated by the reagent which is used, and secondly, ofte not capable of being so recipitated.

As an example of the t, case, if a solution of iron and nickel is treated with calcium hydrate, which reagent will precipitate either metal alone, and the reagent is added in the proper amount to precipitate the iron, the llOIl precipitate will always carr down some insoluble nickel. As an examp e of the second case, if a solution of iron and nickel, with ammonium chlorid present, be treated with ammonium hydrate, which reagent will precipitate iron alone with ammonium chlorid, but which will not precipitate nickel alone with ammonium chlorid, and the reagent be added in the proper amount to preci itate the iron, the iron preci itate will a ways carry down some insolub e nickel. In both of these cases, if the nickel were not present in the original solution in an amount much greater than the iron, the iron will predominate in the preci itate because ferric hydrate is more inso uble than nickel hydrate,

The usual wa in which these precipitations would be ma e in the laboratory would be to add to the solution of iron and nickel in a beaker the proper amount of reagent and agitate by means of a stirring rod until the mixture became homogeneous and then stop, the idea being that the precipitation of a certain amount of nickel in the iron was unavoidable and irremediable except, of

11 even if said second metal is whereby a course, by the use of some solvent (such as ammonium hydrate) which will dissolve nickel precipitates but will not dissolve iron precipitates.

We are not aware that it has been known that a slow subsequent action is possible by agitating the mixture in the presence of an excess of soluble salt of the metal forming the more insoluble precipitate, in this case iron, where by excess of soluble salt is meant, more salt than is necessary to enter into the the reaction under discussion, that of precipitation of the iron as insoluble salt with attendant solution of the nickel. It has always been considered impossible to get the iron out free of copper and nickel and in fact has been'considered necessary to take out the iron by means of a weak alkali (followed by a strong alkali for the nickel) or else the iron preci itate would containa very large amount 0 nickel.

By our im roved method the iron may be reci itated y as stron an alkali as is used or t e nickel, in fact a three metals, iron,

copper and nickel, may be removed by the same reagent which may be strong or weak. The old method of pur' g such a precipitate of the included meta such, for instance, as the purifying 'of ferric hydrateof inclusion of nickel hydrate, is to se arate the-precipitate from the solution, issolve it, for 1nstance in an acid, and then re recipitate with a propler amount of a suitab e reagent,

the iron is a ain thrown down and containing some nicke but not so much of the latter as before, the difierence of nickel being left in the second filtrate. The reason why the nickel exists in the second filtrate in less quantities than it does in the first is because in the acid solution it is in a more disseminated condition with regard to the iron than it was in the original so ution, there being less nickel present, and only part of the nickel present being thrown down each time. Therefore a suflicient number of se arations in sufliciently dilute solutions wi accomplish a quantitative separation, giving, all the nickel in the united filtrate which will be very dilute. This method is commonly used in quantitative analysis, and ordinarily four separations under good conditions are suiiicient. Our method, however, as ordinarily practiced, while giving the precipitate practically pure, does not at one time remove from the solution all of the metal forming the most insoluble precipitate, because of the fact that the precipltate is afterwards purified by agitation in a solution containing an excess of a soluble salt of the metal which is being urified. Our method is, therefore, not a p lcable to quantitative analysis, but is ap lcable to the commercial se aration of meta from a solution which is eing supplied continuously to the cycle.

The following description sets forth in detail certain modes of carrying out the invention, such disclosed modes constituting but a part of the various ways in which the principle of the invention may be used.

The apparatus required to carry out our improved processconsists of any suitable form of agitating and containing tanks, and filtering or settling devices, and is the same for the separation of iron, copper and nickel as it is for other metals and substances.

We have devised several methods for carrying out our invention; each of which de ends for its improved result of obtaining su stantially ure precipitates upon the com arative so ubilities of the substantially inso uble precipitates which are thrown down from the original solution when a reagent is added thereto in an amount equal to the chemical equivalent of the metal which forms the more insoluble precipitate. Such invention is thus broadly set forth in our pending application Serial No. 300,728,

filed February 12, 1906, Where three of the several methods to which allusion is here made are described indetail. This our present application relates specifically to one of these methods only. In this method, the solution of iron, copper and nickel is agitated in any suitable vessel with owdered limestone in an amount equal to t e chemical equivalent of the iron present in the solution, the result of which is the almost immediate precipitation of most of the iron as a hydrate, but even in a dilute solution there is some copper and nickel thrown down as basic carbonates. A prolonged agitation of the precipitates in the original solution purifies the iron precipitate of the included cop er and nickel basic carbonates because of t e comparative solubilities of the ferric hydrate and said basic carbonates, according to the following order of insolubility:

CuCl a little FeCl I 3CuCO .CuO I-I 4FeOl 311,0 agitated 6CuCl 3C0 4FeO H 3NiCO,.NiO H lFeCl 3H O agitated found to be substantiallly 7 pro v After a rolonged agitation with a proper amount 0 reagent, the ferric hydrate is free of the included cop r and nicke basic carbonates and the sofiion is found to be free of iron. The precipitate is separated and washed by any convenient method from the copper and nickel solution, the latter going mto any suitable container. This copper and nickel solution is 'tated with calcium hydrate to the chemic e uivalent ofthe copper present, the result eing the almost immediate precipitation of most of the -copper as hyrate, which latter contains some nickel as hydrate. A prolonged agitation of this impure cop r prerlslipitate 1n the copper and nickel so ution w' purify said precipitate of the nickel because of the comparative solubilities of the recipitated hydrates. The excess of the so uble copper sa t in the original solution thus slowly dissolves the nickel hydrate contained in the insoluble cupric hydrate and precipitates in turn more cupric hydrate. The reactions are as follows:

CuCl,+ NiOl', CaO,H OuO H CaOl,+

NiCl5+ a little Cubl +a little NiO H,.

NiO,H, CuCl agitated OuO H NiCl After a prolonged agitation with the er amount of'calcium hydrate the cupric rate is found to be substantially free of t e nickel hydrate and the solution is free of copper. The cupric hydrate is separated and washed from the nickel solution, the latter going into any suitable container. This nickel solution is treated with suitable reagent, such as calcium hydrate, the 'result bein the almost immediate precipitation of all 0 the nickel present, free from the iron and copper, without prolonged agitation, the

' reaction being:

NiCl, OaO,H, NiO H, CaCl,,.

also. to thus separating aluminum and combinations of these two metals, as also iron in both conditions of oxidation. So, too, what has been said with regard to the se aration of nickel will apply equally where co alt, and cobalt and nickel together, are to be separated from the other metals referred to resulting mixture homogeneous.

We mean by the term chemical e uivalent of a reagen such an amount 0 that reagent as actually andv finally enters into the reaction, since the cores of some particles of insoluble reagent might not react andit would be necessary, therefore,fto add the reagent in a -quantity in excess of that representing the theoretical chemical equivaent.

We mean by the term insoluble recipitates those that are more insolub 0 than the hydrates of barium and calcium, for instance, the hydrates and carbonates of iron, aluminum, copper, nickel, etc.

It is a well-known law, of course, that the insoluble compounds tend to form'and precipitate; for instance, the following reaction naturally takes place immediately:

broad head, but rather is a simultaneous dissolving to thevery slight amount possible, of the more soluble component of a substantially insoluble mixture, and a precipitation from the solution of the other metal which is contained also as the more insoluble com ound in the original insoluble mixture.

T ere are several reagents any one of which might be used in certain steps of our process. Instead of calcium carbonate in the precipitation of the iron, other alkaline and alkaline earth carbonates and hydrates mag be substituted, such as calcium hydrate an sodium hydrate. For the calcium h drate in the co per preci itation there mig t be substitute such a kaline or alkaline earth carbonates and hydrates as calcium carbonate, sodium hydrate and sodium carbonate. If any one of thethree metals, iron, copper and nickel, is absent, the other two may be separated and purified as described above, simply omitting the steps required by our process for that particular metal which is absent. For instance, iron could be separated from nickel alone; from copper alone;

or copper'could be separated from nickel alone.

It sometimes ha pens that a change of temperature from t e ordinary is an aid to the separation b causing an ap reciable difference in the slight solubilities of the two insoluble substances, which have, at ordinary temperatures, solubilities so nearly identical that an economic separation is prevented. For instance, compounds of cobalt and nickel might have substantially the same solubilities at a temperature of 20 degrees; whereas at 60 degrees their solubilities might be so difierent as to allow of an economic separation by our process. If, at any time, more of the reagent is added than the chemical equivalent of the metal to be precipitated,

the condition of equilibrium can be restored by the addition of more of the original solution, which amounts, in effect, to the adding of the chemical equivalent.

Our method does not give dilute solutions and yet we obtain purepreci itates of the iron, copper and nickel instead 0 the impure preci )ltittBS which are obtained by present methods, and the basic principle of our rocess is the purification of any precipitate metal or substance of the incluslons of other preci itated metals or substances slightly more sol ble than the first, all of the recipitates being substantially insolublealiliough nothing is absolutely insoluble in a solvent-*bymeans of agitating such impure precipitate in a solution containin soluble salts of the more insoluble metal. We do not confine ourselves to the use of water as a solvent for obtaining the original solution. Where both or all of the metals in solution are capable of being precipitated by the reagent used, there has often been left and lost as much as 25% impurity, for instance, of nickel in the iron; whereas, we are able, by our method, to free the iron precipitate entlrely of the nickel impurity by asufliciently long and vigorous agitation. Our method, of course, works best on substances which, although insolu-' ble, are colloidal and freely disseminated, since, thus, infinitely great surfaces are constantly presented for solution and subsequent immediate action of'the soluble salt.

We wish to point out that, if the addition of the required amount of reagent be made so gradually that it extends over a considerable length of time duri which agitation is going on, this amounts 1n substance to addmg the required amount of reagent and then subjectln the mixture to prolonged agitation/Z l inally we should state that by the expression, t e metal which is being purified, as used in the description and claims, we mean the metal which we are trying to remove as a precipitate free of the other metals.

Other modes of a plying the principle of our invention may e employed instead of the one explained, change eing made as regards the process herein disclosed, provided the step or steps stated by any one of the following claims or the equivalents of such stated step or steps be employed.

We therefore particularly point out and distinctly claim as our invention 1. In a rocess of separating one metal substantial y free from another, such metals bein contained in a solution, the steps whicl consist in adding to the solution a reagent capable ofproducing a relatively insoluble precipitate with one of the metals, such reagent being added in an amount equal to the chemical equivalent of said one metal; and then agitating the resultant mixture until any inclusions of the other metals are substantially dissolved out.

2. In a rocessof separating metals, each substantia ly free from the others, such metals being contained in a solution, the steps which consist in re eating the following cycle of operations unti each metal has been successively separated out; adding to the solution a reagent capable of producing a relativel insoluble precipitate with that metal whic it is desired to separate out, such reagent being added in an amount equal to the chemical equivalent of such metal; agitating the resultant mixture until such precipitate is purified of inclusions of the other metals; and then removing the precipitate.

3. In a rocess of separating one metal substantial y free from another, such metals bein contained in a solution, the steps which consist in addin to the solution a reagent capable of pro ucing substantially insoluble precipitates with said metals, one precipitate, however, varying from the other in its degree of solubility, such reagent bein added in an amount equal to the chemica equivalent of one of said metals; and then agitatin the resultant mixture until the more soluble precipitates are substantially re-dissolved.

4. In a process of se arating metals in solution, the steps whic consist in adding to the solution a reagplnt capable of formin e preclpitates wit substantially insolu said metals, one reci itate, however, bein slightly less solu le t an the others, sue reagent being added in an amount equal to the chemical equivalent of such less soluble preci itate; and then purifying such less solub e precipitate of the inclusions of the other precipitates by agitating the same in a solution of the metal formin such less soluble precipitate until such ot er precipitates are substantially redissolved.

5. In a process of se arating metals in solution, the steps whic consist in adding to the solution a reagent capable of formin substantially insolub e preci itates with sai metals, one precipitate, owever, bein slightly less soluble than the others, suc reagent being added in an amount equal to the chemical equivalent of such less soluble precipitate; and then purifying such less soluble precipitate of the inclusions of the other precipitates by agitatin the same in a solution containing soluble saIts of the metal forming such less soluble precipitate until such other precipitates are substantially redissolved.

6. In a process of separating metals in solution, the steps which consist in adding to the solution a ma ent capable of forming substantially inso uble precipitates with said metals, one precipitate, however, bein producing oranos uble precipitate of the inclusions of the other the other precipitates are substantially redimolved. 1

7. In a process of separating metals in solution, the steps which consist in adding to the solution a re ent capable of forming sub,

stantially insouble precipitates with said metals, one lprecipitate, however, being slightl less so uble than the others, such ret added in an amount equal to the c emical uivalent of the metal roduc' such less so uble precipitate; pu suc less soluble precipitate of the inclusions of the other precipitates by agita the mixture resulting upon the addition 0 such reagent until such other preci itates are redissolved;

- removing such fpurifi precipitate; and then repeating the oregoing series of steps with th remamtrzg solution until all the metals are so am 8. a rocess of separating two metals in solution, e steps which consist in adding to the solution a reagent capable of f0 substantially insoluble precipitates with saig metals, oneprecipitate, however, varying slightly from the other in its degree of solubihty, such reagent being added in an amount equal to the chemical e uivalent of the metal tproducing the less solu 1e precipitate; and en purifying such less solu le precipitate of the inclusions of the other by agitating the same in a solution forming such less soluble precipitate until such inclusions are redissolved.

9. In a recess of separating two metals in solution, e steps which consist in adding to the solution a reagpnt capable of f0 substantially in'solu le precipitates with said metals, one precipitate, however, varying slightly from the other in its degree of solubihty, such reagent being added in an amount equal to the chemical uivalent of the metal roducing the less solu le recipitate; and en uriiying such less solu le precipitate of the inclusions of the other by agitatifi the same in a solution containing soluble ts of the metal forming the less soluble precipitate until such inclusions are redissolved.

10. In a process of separating two metals in solution, the steps which consist in addi to the solution a reagent capable of formin substantially insolub e precipitates with sai metals, one precipitate, however, varying sli htly from the other in its degree of solubifi such reagent being added inanamount equal to the chemical equivalent of the metal the less soluble recipitate; and then purifying such less so uble precipitate of the inclusions of the other b agitating the mixture result' upon the a ditlon of such reagent until suc inclusions are redissolved.

11. In a process of separating iron and nickel in solution, the steps which-consist in adding to the solution a reagent capable of producing an insoluble precipitate -with the rron, such reagent being added in an amount limited to the chemical equivalent of the iron; and then agitating the mixed solution and precipitate until any inclusions of nickel are redissolved.

12. In a process of' separatin iron and nickel in solution, the steps whic consist in adding to the solution a reagent capable of producing substantiall insoluble precipitates with said iron an nickel, the iron precipitate, however, being slightl less soluble than the nickel precipitate, suc reagent being added in an amount limited to the chemical equivalent of the iron; and then purifying such iron precipitate of inclusions of nickel precipitate by agitating the mixedsolution and precipitate until any inclusions of nickel pro redissolvepl.

13. n a rocess 0 se arat' iron, co er and nickel in solution, the si dgs which dhn sist in adding to the solution a rea ent capable of producing a relatively inso uble preci itate with the iron, such reagent bein arfded in an amount limited to the chemical eqluivalent of the iron; agitating the mixed so ution and (precipitate until any inclusions of copper an nickelare redissolved; removing the iron precipitate; adding to the filtrate a reagent capab e of producing a relativel insoluble precipitate with the cop er, suc reagent being added in an amount lmited to the chemical equivalent of the copper; and

then agitating the mixed solution and pre-' cipitate until any inclusions of nickel are redissolved.

14. In a process of separating iron, copper, and nickel in solution, the steps which consist in adding to the solution a reagent capable of producing substantiall insoluble precipitates with said metals, t e iron recipitate however, being slightly less solub e than the co per and nickel precipitate, such reagent eing added in an amount limited to the chemical equivalent of the iron; agitating the mixed solution and precipitate until any inclusions of cop er and mckel are redissolved removing t e iron precipitate; adding to the filtrate a reagent capable of producing a substantially insoluble precipitate with the copper and nickel, the copper nickel precipitate, suc reagent being added in an amount hmited to the chemical e uivalent of the copper; agitating the mixe solu tion and precipitate until any inclusions of nickel are redissolved; and then removing the co er precipitate.

15.. n a process of separating iron and nickel in solution, the steps which consist in adding calcium carbonate in an amount eqpal to the chemical equivalent of the iron, w ereby the major portion of such iron is recipitate, however, being slightl less solub e than the preci itated as hydrate together with a sma portion of nickel as basic carbonate;

.and then urifying such iron precipitate of the inclusions of the nickel precipitate by agitating the mixed solution and Ereci itate until the remainder of the iron in t e so ution is preci itated.

16. n a process of se arating lron, copper, and nickel 1n solution, t e steps which consist in adding calcium carbonate to the solution in an amount equal to the chemical equivalent of the iron, whereby themajor portion of such iron is precipitated as hydrate together with small ortions of copper and nickel as basic car onates; urifying such iron preci itate of the incluslons of copper and nicke precipitate by agitating the mixed solution and precipitates until the remainder of the iron in the solution is precipitated; removing the iron precipitate; adding to the remaining solution calcium hydrate to the chemical equivalent of the copper therein, whereby the major portion of such cop er, together with some nickel, is precipitate as hydrate; purifying such copper precipitate of the inclusions of nickel precipitate by agitating the mixed solution and precipitates until the remainder of the copper in the solution is precipitated; and then removing the co per precipltate.

lgned by HERBERT H. Dow, this 15th day of March, 1907.

HERBERT H. DOW. Attested by DS. DAVIES, JNo. F. 'OBERLIN.

Signed by WALTER S. GATES, this 4th day of January, 1907.

WALTER S. GATES. Attested by- A. N. PATRIARCHE, THOS. Gmswonn, Jr. 

